Silicone (meth)acrylamide monomer, polymer, ophthalmic lens, and contact lens

ABSTRACT

The present invention relates to a silicone (meth)acrylamide monomer, and this silicone (meth)acrylamide monomer is particularly suitable for use in contact lenses, intraocular lenses, artificial cornea, and the like.

RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 13/048,469, filedMar. 15, 2011; which claims priority to Japanese Patent Application No.JP-2010-061991 filed Mar. 18, 2010.

BACKGROUND OF THE INVENTION

The present invention relates to a silicone (meth)acrylamide monomerwith a straight chain siloxanyl group and preferably with a hydroxylgroup in a molecule. A polymer obtained by polymerizing this monomer issuitable for use in various medical implements such as ophthalmiclenses, endoscopes, catheters, transfusion tubes, gas transport tubes,stents, sheaths, cuffs, tube connectors, access ports, drainage bags,blood circuits, wound covering material, and various types of medicinecarriers, but is particularly suitable for contact lenses, ophthalmiclenses, and artificial corneas.

DESCRIPTION OF THE RELATED ART

In recent years, silicone hydrogels obtained by copolymerizing asilicone monomer, a hydrophilic monomer, and a cross-linking agentmonomer have become known as materials for contact lenses that are usedfor continuous wear. Patent document 1 discloses silicone acrylamidemonomers expressed by the following formulas (x1) and (x2) as suitablefor use in making silicone hydrogels.

However, the silicone region of the silicone acrylamide monomer shown inpatent document 1 is a branched siloxanyl group, so polymers obtained bypolymerizing these monomers may have inferior shape recovery properties.Herein, branched refers to a condition where the Si—(O—Si)_(x) bond(where x is an integer 1 or higher) beginning at the silicon atom thatis bonded to the carbon backbone of the molecule is not a continuoussingle strand. Therefore, if a straight chain siloxanyl group is used,hydrophobicity will be increased and there is a concern thatcompatibility with hydrophilic substances will be inferior.

Furthermore, the composition of patent document 1 contains approximatelyfrom 30 to 40 weight parts of methacrylate ester. While the acrylamidemonomer has a higher polymerization rate constant than the methacrylateester during homopolymerization, the rate of acrylamide and methacrylatecopolymerization is significantly lower and as a result thepolymerization rate of the entire system will be reduced.

On the other hand, patent document 2 discloses a silicone acrylamidemonomer expressed by the following formulae (y1) and (y2), and asilicone hydrogel made from this monomer and a hydrophilic acrylamidemonomer.

Acrylamide monomers account for the majority of the composition that isused in the silicone acrylamide monomer disclosed in patent document 2,and a higher polymerization rate for the entire system is anticipated.However, the silicone region of these monomers also has a branchedsiloxanyl group, so polymers obtained by polymerizing these monomersdisplay inferior shape recovery. Furthermore, the amido bond of theacrylamide group has high hydrophilicity, and therefore providing atransparent lens may be difficult from the perspective of achieving botha sufficient amount of silicone component to provide high oxygenpermeability and providing sufficient water content to provideflexibility to the lens. In particular, achieving a transparent lens isespecially difficult if an internal wetting agent is added in order toincrease the wettability of the surface.

REFERENCES OF RELATED ART Patent Documents

-   Patent Document 1 US2005/0176911-   Patent Document 2 Japanese Unexamined Patent Application H10-212355

SUMMARY OF THE INVENTION

The present invention relates to silicone (meth)acrylamide monomers witha fast polymerization rate, and a polymer obtained thereby havingfavorable transparency and shape recovery.

The present invention further relates to the following compositions.Namely,

(1) A silicone (meth)acrylamide monomer comprising a (meth)acrylamidegroup and a straight chain siloxanyl group having two or more —OSirepeating units in a molecule.

(2) The silicone (meth)acrylamide monomer according to (1), wherein thesilicone (meth)acrylamide monomer further comprises at least onehydroxyl group.

(3) The silicone (meth)acrylamide monomer according to (2), expressed bythe following general formula (a).

(R represents a hydrogen atom or a methyl group; R¹ represents ahydrogen atom or an alkyl or an aryl group with between 1 and 20 carbonatoms which may be substituted with hydroxyl, acid, ester, ether, thioland combinations thereof; R² represents a C₁₋₁₀ alkylene group orarylene group that may be substituted with hydroxyl acid, ester, ether,thiol and combinations thereof; wherein at least one of either R¹ or R²has a hydroxyl group. R³ to R⁹ independently represent a C₁₋₂₀ alkylgroup or an aryl group with between 1 and 20 carbon atoms, either ofwhich may be substituted with fluorine, hydroxyl, acid, ester, ether,thiol and combinations thereof, and n is an integer in a range from 1 to10.The present invention further relates to polymers, ophthalmic lenses andcontact lenses obtained by polymerizing a monomer mixture comprising atleast one silicone (meth)acrylamide monomer as described herein.

DETAILED DESCRIPTION OF THE INVENTION

The present invention contains the silicone (meth)acrylamide monomer ofthe present invention and therefore can provide a silicone hydrogel witha high acrylamide monomer content, that is transparent, and that has anexcellent balance between water content and wettability. The polymerobtained by polymerizing this silicone hydrogel is suitably used forvarious types of medical implements, particularly for ophthalmic lensessuch as contact lenses, intraocular lenses, and artificial cornea, andespecially for contact lenses.

A silicone (meth)acrylamide monomer of the present invention has a(meth)acrylamide group and a straight chain siloxanyl group in amolecule, and preferably has at least one hydroxyl group in a molecule.A siloxanyl group refers to a group having at least one Si—O—Si bond,“straight chain” refers to a structure where a bond is formed in asingle line beginning with a silicon atom that is bonded to an alkylgroup which has a (meth)acrylamide group, or in other words a silicone(meth)acrylamide monomer having a straight chain siloxanyl group refersto a structure expressed by the following general formula (p)

In formula (p), R^(p) represents an alkyl group with a (meth)acrylamidegroup. R^(a) through R^(g) represent groups that do not contain asilicon atom. x represents an integer 2 or higher. Unlike the silicone(meth)acrylamides of the present invention, silicone (meth)acrylamidesof the prior art contained at least a portion of the silicone in apendant chain. In formula (p), x represents an integer 2 or higher, andif x is too small, sufficient oxygen permeability will not be achieved,but if too large, compatibility with the hydrophilic monomer willdecrease, and achieving a transparent lens will be more difficult.Therefore, in some embodiments, x is a value between 3 and 7, between 3and 6, and between 3 and 5. Furthermore, preferably x does not have adistribution in order to increase a reproducibility of the physicalproperties of the polymer obtained. For the present invention, thephrase “does not have a distribution” indicates a condition whereinvarious peaks for different values of x, a ratio of the largest peak is80% or higher, as measured by GC for the case of a monomer that can bemeasured using gas chromatography (GC) (FID analyzer), or as measured byliquid chromatography (LC) (RI analyzer) for the case of a monomer hassuch high boiling point that cannot be measured using GC.

Furthermore, in this specification, (meth)acryl refers to acryl andmethacryl and (meth)acrylamide refers to acrylamide and methacrylamide.

The silicone (meth)acrylamide monomer of the present invention withouthydroxyl group includes the monomer expressed by the following formulae(s1), (s5) and (s6);

Of these monomers, the monomers expressed by the formulae (s5) and (s6)are more preferable from the perspective of low modulus of the siliconehydrogel obtained.

With the present invention, there is concern that a hydrophobicity willincrease and a compatibility with hydrophilic substances will beinferior if the monomer contains a straight chain siloxanyl group, but ahydrophilicity can be increased by having an amido bond and a hydroxylgroup. However, if a number of hydroxyl groups is too high, an elasticmodulus of the polymer will be undesirably high and therefore the numberof hydroxyl groups per monomer unit is in one embodiment between 1 and6, and in another between 1 and 3, further 1 or 2, and, wherewettability (low contact angles) of the polymer obtained is particularlyimportant, 2.

Furthermore, if a branched siloxanyl group is present in addition to thestraight chain siloxanyl group, the hydrophobicity may be undesirablyhigh. Therefore, in one embodiment a branched siloxanyl group is presentin an amount less than about 15 weight % based upon the polymerizationcomponents, and in other embodiments a branched siloxanyl group is notpresent.

The silicone (meth)acrylamide monomer of the present invention has a(meth)acrylamide group as a polymeric group in order to increase apolymerization rate, and therefore an increased polymerization rate canbe anticipated. When an acrylamide monomer is used as a hydrophilicsubstance, this effect is particularly prominent. This increase inpolymerization rate decreases the cure time needed to complete thepolymerization and yield the final material. Of acrylamide groups andmethacrylamide groups, acrylamide groups are preferable from aperspective of further increasing the polymerization rate. As describedabove, ensuring transparency is difficult if an amide group is present,but if a hydroxyl group is present, a drop in the transparency due tothe presence of an amide group can be prevented. The details areunclear, but it is thought that in addition to acting as acompatibilizer, the hydroxyl group also acts to increase wettability.

An example of a preferable structure of the silicone (meth)acrylamidemonomer of the present invention with at least one hydroxyl group is themonomer expressed by the following general formula (a).

In formula (a), R represents a hydrogen atom or a methyl group. In oneembodiment, R is a hydrogen atom and the silicone (meth)acrylamidedisplays an increased polymerization rate. In formula (a), R¹ representsa hydrogen atom or an alkyl or an aryl group with between 1 and 20carbon atoms which may be substituted with hydroxyl, acid, ester, ether,thiol and combinations thereof.

In one embodiment, R¹ is a hydrogen atom or an alkyl having between 1and 5 carbon atoms which may be substituted with hydroxyl, acid or estergroups. In another embodiment R¹ is an alkyl group having 1-5 carbonatoms, and may be unsubstituted or substituted with at least onehydroxyl group. Examples of R¹ include hydrogen atoms, methyl groups,ethyl groups, propyl groups, n-propyl groups, i-propyl groups, n-butylgroups, s-butyl groups, t-butyl groups, n-pentyl groups, i-pentylgroups, s-pentyl groups, neopentyl groups, hexyl groups, heptyl groups,octyl groups, nonyl groups, decyl groups, dodecyl groups, eicosylgroups, phenyl groups, naphthyl groups, all of which may be substitutedas described above, and the like. In one embodiment, R¹ is selected frommethyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butylgroups, s-butyl groups, or t-butyl groups, any of which may be hydroxylsubstituted. In another embodiment R¹ is selected from hydrogen atoms,methyl groups, ethyl groups. Hydrogen atoms, methyl groups and ethylgroups provide the silicone (meth)acrylamide monomer with increasedhydrophilicity. Examples of hydroxyl substituted R¹ groups include2-hydroxyethyl groups, 2-hydroxypropyl groups, 3-hydroxypropyl groups,2,3-dihydroxypropyl groups, 4-hydroxy butyl groups,2-hydroxy-1,1-bis(hydroxymethyl)ethyl groups, 2-hydroxymethylphenylgroups, 3-hydroxymethylphenyl groups, 4-hydroxymethylphenyl groups, andthe like. In one embodiment R¹ is selected from 2-hydroxyethyl groups,2-hydroxypropyl groups and 2,3-dihydroxypropyl groups, and in anotherembodiment R¹ is a 2,3-dihydroxypropyl groups. 2,3-dihydroxypropylgroups provide the silicone (meth)acrylamide with increasedhydrophilicity. Furthermore, if the transparency of the polymer obtainedby polymerizing the silicon (meth)acrylamide monomer must be furtherenhanced, R¹ is preferably not a hydrogen atom.

R² represents a bivalent C₁₋₁₀ alkylene group or aryl group that may besubstituted with hydroxyl, acid, ester, ether, thiol and combinationsthereof. In another embodiment R² is selected from C₁₋₅ alkylene groups,which may be unsubstituted or substituted with hydroxyl, ether groupsand combinations thereof. In another embodiment R² is selected from C₂₋₅alkylene groups, which may be unsubstituted or substituted withhydroxyl, ether groups and combinations thereof, and in yet anotherembodiment, R² is a C₃ alkylene groups, which may be unsubstituted orsubstituted with hydroxyl, ether groups and combinations thereof. In yetanother embodiment R² is a group of formula (d):—CH₂CH(OH)CH₂—  (d)Or the groups expressed by the following formula (b):—CH₂CH(OH)CH₂OCH₂CH₂CH₂—  (b)

Examples of suitable R² groups include methylene groups, ethylenegroups, propylene groups, butylene groups, pentalene groups, octalenegroups, decylene groups, and phenylene groups, any of which may beunsubstituted or substituted with at least one hydroxyl and, a grouprepresented by the following formula (d):—CH₂CH(OH)CH₂—  (d)and the groups expressed by the following formula (b):—CH₂CH(OH)CH₂OCH₂CH₂CH₂—  (b)

These alkylene and arylene groups can be straight or branched. Of these,ethylene, propylene, butylene, the groups expressed by formulae (d), and(b) are preferable in some embodiments and silicone (meth)acrylamidescontaining them polymerize to form a polymer with low elastic modulus.In another embodiment R² is selected from an ethylene group, propylenegroup, or butylene group, and in another embodiment, R² is n-propylenegroup, from a perspective of achieving a balance between hydrophobicityand a lowered elastic modulus for the polymer obtained by polymerizingthe silicone (meth)acrylamide monomer.

In formula (a), R³ through R⁹ independently represent an alkyl group oran aryl group with between 1 and 20 carbon atoms either of which may besubstituted with fluorine, hydroxyl, acid, ester, ether, thiol andcombinations thereof. Examples of R³ through R⁸ include hydrogen atoms,methyl groups, ethyl groups, propyl groups, n-propyl groups, i-propylgroups, n-butyl groups, s-butyl groups, t-butyl groups, n-pentyl groups,i-pentyl groups, s-pentyl groups, neopentyl groups, hexyl groups, heptylgroups, octyl groups, nonyl groups, decyl groups, dodecyl groups,eicosyl groups, phenyl groups, naphthyl groups, any of which may besubstituted by fluorine, hydroxyl or combinations thereof and the like.In some embodiments, an alkyl group with between 1 and 4 carbon atoms ispreferable, and a methyl group is most preferable, from a perspective ofincreasing the oxygen permeability. R⁹ independently represents an alkylgroup or an aryl group with between 1 and 20 carbon atoms. Examples ofR⁹ include hydrogen atoms, methyl groups, ethyl groups, propyl groups,n-propyl groups, i-propyl groups, n-butyl groups, s-butyl groups,t-butyl groups, n-pentyl groups, i-pentyl groups, s-pentyl groups,neopentyl groups, hexyl groups, heptyl groups, octyl groups, nonylgroups, decyl groups, dodecyl groups, eicosyl groups, phenyl groups,naphthyl groups, any of which may be substituted by fluorine, hydroxylor combinations thereof and the like. With regards to R⁹, an alkyl groupwith between 1 and 4 carbon atoms is preferable, and in someembodiments, an n-butyl group, s-butyl group, or a t-butyl group, whichmay be unsubstituted or hydroxyl substituted are most preferable, basedon a balance between the oxygen permeability and a hydrolysis resistanceof the siloxanyl group. In other embodiments R⁹ may be methyl or ethyl.

In formula (a), n represents an integer between 1 and 10, and if n istoo small, desirable oxygen permeability may not be achieved, but if toolarge, compatibility with the hydrophilic monomer will decrease, andachieving a transparent lens will be more difficult. Therefore in someembodiments n is a value between 2 and 6, between 2 and 5, and between 2and 4. Any of the lower limit values and any of the preferred upperlimit values can be combined together. Furthermore, preferably n doesnot have a distribution in order to increase a reproducibility of thephysical properties of the polymer obtained. For the present invention,the phrase “does not have a distribution” indicates a condition whereinvarious peaks for different values of n, a ratio of the largest peak is80% or higher, as measured by GC for the case of a monomer that can bemeasured using gas chromatography (GC) (FID analyzer), or as measured byliquid chromatography (LC) (RI analyzer) for the case of a monomer hassuch high boiling point that cannot be measured using GC.

The silicone (meth)acrylamide monomers of the present invention can beprepared by any method known to those of skill in the art of syntheticorganic chemistry. An example of preparation method for silicone(meth)acrylamide monomer expressed by the formula (a)

comprises hydrosilylation of the compound expressed by the followingformula (a10)

with a linear siloxane expressed by the following formula (all)

and comprises (meth)acrylation of the compound expressed by thefollowing formula (a12)

obtained from the hydrosilylation. In the formula (a10), Q¹ comprise acarbon-carbon double bond and is converted to R² of the formula (a) byhydrosilylation.

One of more specific example of preparation method for a silicone(meth)acrylamide monomer of the present invention is a method for themonomers expressed by the following formula (a20).

The preparation method comprises ring-opening reaction of epoxide byamine, protection of hydroxyl group(s), hydrosilylation, acrylation, andde-protection of hydroxyl group(s). In the formula (a20), R, R², R³through R⁹, and n are the same with those in the formula (a) above, and—CH₂CH(OH)R¹¹ in the formula (a20) represents R¹ in the formula (a).

In the ring-opening reaction of epoxide by amine at the first step, acompound expressed by the formula (a23) can be obtained by reacting anepoxide expressed by the following formula (a21) with an amine expressedby the following formula (a22).

Q²-NH₂  (a22)

In the formulae (a22) and (a23), Q² comprises a carbon-carbon doublebond and is converted to R² in the formula (a20) by hydrosilylation ofthe double bond.

The (a22)/(a21) ratio of the reaction is preferably from about 1 toabout 50, more preferably from about 1.5 to about 30, and mostpreferably from about 2 to about 15 to reduce di-substituted andtri-substituted amine by-product. The temperature of the reaction ispreferably from about −20° C. to about 100° C., more preferably fromabout 0° C. to about 50° C., and most preferably from about 20° C. toabout 40° C. to avoid vaporization of amines. The time of the reactionis from about 1 hour to about 72 hours.

In the second step, hydroxyl group(s) of the compound (a23) from thefirst step may be protected to avoid side-reaction of hydrosilylation.One suitable example of protecting groups is trimethylsilyl group, whichcan protect and de-protect in mild condition. Any known reagents fortrimethylsilylation of hydroxyl group can be used, such astrimethylsilyl chloride, trimethylsilyl trifluoromethanesulfonate,N-Methyl-N-trimethylsilylacetamide, and hexamethyldisilazane. Amongthese, hexamethyldisilazane is preferable because no salt remains afterreaction. The temperature of the trimethylsilylation reaction withhexamethyldisilazane is from about 40° C. to about 150° C., morepreferably from about 50° C. to about 130° C., and most preferably fromabout 70° C. to 120° C., and the time of the reaction is from about 0.5hour to about 5 hours. Purification by vacuum distillation is preferablebefore the next step.

In the third step, the compound expressed by the following formula(a24),

wherein P¹ represents a protecting group, from the second step isreacted with linear siloxane expressed by the following formula (a25).

wherein R³ through R⁹, and n are the same in the formula (a). The ratioof (a25)/(a24) is between about 0.5 and about 2.0, more preferablybetween about 0.8 and about 1.2, and most preferably between 0.9 and1.1. Suitable catalysts include platinum (0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, platinum (0)1,3-dimethyl-1,3-divinyldisiloxane, hydrogen hexachloroplatinate (IV),and more preferably platinum (0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, platinum (0)1,3-dimethyl-1,3-divinyldisiloxane. The catalyst is used in an amountbetween about 1 ppm and about 10000 ppm, more preferably between about 5ppm and about 5000 ppm, and most preferably between about 10 ppm andabout 1000 ppm. The temperature of the reaction is preferably betweenabout −20° C. to about 180° C., more preferably between about −10° C. toabout 150° C., and most preferably between about 0° C. to about 130° C.

In the fourth step, the amino group of the compound expressed by thefollowing formula (a26)

from the third step can be reacted with an acrylating agent, such as(meth)acryloyl halide, (meth)acrylic anhydride. When (meth)acryloylhalide is used, the temperature of the reaction is preferably betweenabout −80° C. to about 40° C., more preferably between about −40° C. toabout 30° C., and most preferably between about −20° C. to about 10° C.Inhibitor may be added in an amount between 1 ppm and 5000 ppm, morepreferably between 10 ppm and 1000 ppm, most preferably 50 ppm and 500ppm to avoid polymerization during monomer synthesis. Suitableinhibitors include hydroquinone monomethylether, butylatedhydroxytoluene, mixture thereof and the like. As a result of this step,a monomer expressed by the following formula (a27)

is obtained. The monomer (a27) is preferable from the perspective ofcompatibility with wide range of hydrophobic and hydrophilicco-monomers. The monomer (a27) can be de-protected after polymerization,thereby both desirable compatibility in monomer mixture and desirabletransparency of polymer derived from hydroxyl groups can be achieved.

In the fifth step, hydroxyl group(s) of the compound expressed by theformula (a27) is de-protected. The method and condition of de-protectiondepends on P¹. If P¹ is trimethylsilyl group, de-protection with aceticacid in methanol is preferable from the perspective of the mild reactioncondition. The temperature of the reaction is preferably between about20° C. to about 40° C., and the time of the reaction is preferablybetween about 0.5 hour to about 3 hours. After de-protection, theobtained silicone (meth)acrylamide monomer can be purified by variousmethod including column chromatography, vacuum distillation, moleculardistillation, treatment with ion-exchange resin, and the combinationthereof. As a result of this step, silicone (meth)acrylamide monomerexpressed by the formula (a20) is obtained.

Another more specific example of preparation method for a silicone(meth)acrylamide monomer of the present invention is a method for themonomers expressed by the following formula (a30)

The preparation method comprises ring-opening reaction of epoxide byamine, protection of hydroxyl group(s), hydrosilylation, acrylation, andde-protection of hydroxyl group(s). In the formula (a30), R, R¹, R³through R⁹, and n are the same with those in the formula (a) above, and—CH₂CH(OH)R²¹— in the formula (a30) represents R¹ in the formula (a).

In the ring-opening reaction of epoxide by amine at the first step, acompound expressed by the formula (a33) can be obtained by reacting anepoxide expressed by the following formula (a31) with an amine expressedby the following formula (a32).

R¹-NH₂  (a32)

In the formulae (a31) and (a33), Q³ comprises a carbon-carbon doublebond and is converted to R² in the formula (a30) by hydrosilylation ofthe double bond.

The (a32)/(a31) ratio of the reaction is preferably from about 1 toabout 50, more preferably from about 1.5 to about 30, and mostpreferably from about 2 to about 15 to reduce di-substituted andtri-substituted amine by-product. The temperature of the reaction ispreferably from about −20° C. to about 100° C., more preferably fromabout 0° C. to about 50° C., and most preferably from about 20° C. toabout 40° C. to avoid vaporization of amines. The time of the reactionis from about 1 hour to about 72 hours.

In the second step, hydroxyl group(s) of the compound (a33) from thefirst step may be protected to avoid side-reaction of hydrosilylation.One suitable example of protecting groups is trimethylsilyl group, whichcan protect and de-protect in mild condition. Any known reagents fortrimethylsilylation of hydroxyl group can be used, such astrimethylsilyl chloride, trimethylsilyl trifluoromethanesulfonate,N-Methyl-N-trimethylsilylacetamide, and hexamethyldisilazane. Amongthese, hexamethyldisilazane is preferable because no salt remains afterreaction. The temperature of the trimethylsilylation reaction withhexamethyldisilazane is from about 40° C. to about 150° C., morepreferably from about 50° C. to about 130° C., and most preferably fromabout 70° C. to 120° C., and the time of the reaction is from about 0.5hour to about 5 hours. Purification by vacuum distillation is preferablebefore the next step.

In the third step, the compound expressed by the following formula(a24),

wherein P² represents a protecting group, from the second step isreacted with linear siloxane expressed by the following formula (a35).

wherein R³ through R⁹, and n are the same in the formula (a). The ratioof (a35)/(a34) is between about 0.5 and about 2.0, more preferablybetween about 0.8 and about 1.2, and most preferably between 0.9 and1.1. Suitable catalysts include platinum (0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, platinum (0)1,3-dimethyl-1,3-divinyldisiloxane, hydrogen hexachloroplatinate (IV),and more preferably platinum (0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, platinum (0)1,3-dimethyl-1,3-divinyldisiloxane. The catalyst is used in an amountbetween about 1 ppm and about 10000 ppm, more preferably between about 5ppm and about 5000 ppm, and most preferably between about 10 ppm andabout 1000 ppm. The temperature of the reaction is preferably betweenabout −20° C. to about 180° C., more preferably between about −10° C. toabout 150° C., and most preferably between about 0° C. to about 130° C.

In the fourth step, the amino group of the compound expressed by thefollowing formula (a36)

from the third step can be reacted with an acrylating agent, such as(meth)acryloyl halide, (meth)acrylic anhydride. When (meth)acryloylhalide is used, the temperature of the reaction is preferably betweenabout −80° C. to about 40° C., more preferably between about −40° C. toabout 30° C., and most preferably between about −20° C. to about 10° C.Inhibitor may be added in an amount between 1 ppm and 5000 ppm, morepreferably between 10 ppm and 1000 ppm, most preferably 50 ppm and 500ppm to avoid polymerization during monomer synthesis. Suitableinhibitors include hydroquinone monomethylether, butylatedhydroxytoluene, mixture thereof and the like. As a result of this step,a monomer expressed by the following formula (a37)

is obtained. The monomer expressed by the formula (a37) is preferablefrom the perspective of compatibility with wide range of hydrophobic andhydrophilic co-monomers. The monomer (a37) can be de-protected afterpolymerization, thereby both desirable compatibility in monomer mixtureand desirable transparency of polymer derived from hydroxyl groups canbe achieved.

In the fifth step, hydroxyl group(s) of the compound expressed by theformula (a37) is de-protected. The method and condition of de-protectiondepends on P². If P² is trimethylsilyl group, de-protection with aceticacid in methanol is preferable from the perspective of the mild reactioncondition. The temperature of the reaction is preferably between about20° C. to about 40° C., and the time of the reaction is preferablybetween about 0.5 hour to about 3 hours. After de-protection, theobtained silicone (meth)acrylamide monomer can be purified by variousmethod including column chromatography, vacuum distillation, moleculardistillation, treatment with ion-exchange resin, and the combinationthereof. As a result of this step, silicone (meth)acrylamide monomerexpressed by the formula (a30) is obtained.

The polymer of the present invention is obtained via polymerization of abase formulation containing silicone (meth)acrylamide monomer. If arange for the silicone (meth)acrylamide monomer contained is too low,the oxygen permeability of the polymer may be insufficient, but if therange is too high, the hydrophilicity may be insufficient, so themonomer and polymer components in the monomer mixture are between 30 and98 weight %, in some embodiments between about 40 and about 80 weight %,and most in other embodiments between about 50 and about 70 weight %.Lower limit values include about 30 weight %, about 40 weight %, andabout 50 weight %. Upper limit values include about 98 weight %, about80 weight %, and about 70 weight %. Any of the preferred lower limitvalues and any of the preferred upper limit values can be combinedtogether.

The polymer of the present invention is preferably obtained bycopolymerizing at least one hydrophilic monomer with at least onesilicone (meth)acrylamide monomer. Examples of the hydrophilic monomerinclude (meth)acrylate monomer such as 2-hydroxyethyl (meth)acrylate,2-(2-hydroxyethoxy)ethyl (meth)acrylate, glyceryl (meth)acrylate, andpoly(ethyleneglycol) mono(meth)acrylate, polymerizable carboxylic acidmonomer such as (meth)acrylic acid, itaconic acid, crotonic acid, vinylbenzoic acid, N-vinylamide monomer such as N-vinylpyrrolidone,N-vinylformamide, N-vinylacetamide, and N-vinyl-N-methylacetamide, and(meth)acrylamide monomer such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl(meth)acrylamide, (meth)acryloyl morpholine, N-methoxymethyl (meth)acrylamide, N-hydroxymethylacrylamide and the like. Among thesehydrophilic monomers, (meth)acrylamide monomer is preferably used insome embodiments because the polymerization rate of the entire systemwill be increased and copolymerization properties with the silicone(meth)acrylamide monomer will be favorable. Of the (meth)acrylamidemonomers, N,N-dimethylacrylamide is preferable from the perspective ofthe polymerization rate and the balance between hydrophobicity andcompatibility with the silicone monomer.

If a range for the amount of hydrophilic monomer that is used is toohigh, the oxygen permeability may be reduced, but if too low, thesilicone hydrogel may be too hard, and therefore the amount ofhydrophilic monomer is between about 1 and about 50 weight %, in someembodiments between % 10 and 40 weight %, and other embodiments betweenabout 15 and about 35 weight %, based on the monomer and polymercomponent in the monomer mixture. Lower limit values about 1 weight %,about 10 weight %, and about 15 weight %. Upper limit values includeabout 50 weight %, about 40 weight %, and about 35 weight %. Any of thepreferred lower limit values and any of the preferred upper limit valuescan be combined together.

In one embodiment, the polymer of the present invention may use ahydrophilic (meth)acrylamide monomer with two or more hydroxyl groups inthe molecule independently from the aforementioned hydrophilic monomer,or in addition to the aforementioned hydrophilic monomer. In particular,if the hydrophilic polymers described later are used, the transparencyof the polymer may easily deteriorate, so a hydrophilic (meth)acrylamidemonomer is preferably used. When included, the amount of the hydrophilic(meth)acrylamide monomer is between about 1 and about 50 weight %, morepreferably between about 1 and about 30 weight %, and most preferablybetween about 1 and about 15 weight %, based on the monomer and polymercomponent in the monomer mixture. An example of a hydrophilic(meth)acrylamide monomer containing two or more hydroxyl groups in themolecule include the monomers expressed by the following generalformulae (c1) through (c3).

In formulae (c1) through (c3), R¹ independently represents a hydrogenatom or a methyl group. In one embodiment, the hydrogen atoms arepreferable from the perspective of increasing the polymerization rate.Furthermore, of these monomers, the monomers expressed by formula (c1)are preferable from a perspective of increasing the transparency of thepolymer obtained.

In another embodiment, the polymer of the present invention may use ahydrophilic N-(mono-hydroxyl substituted C₁-C₂₀ alkyl)methacrylamide orN-(mono-hydroxyl substituted C₆-C₂₀ aryl)methacrylamide monomerindependently from the aforementioned hydrophilic monomer. Preferablythe polymer may use one of those monomers in addition to theaforementioned hydrophilic monomer. In one embodiment, if thehydrophilic polymers described later are used, the transparency of thepolymer may easily deteriorate, so a hydrophilic methacrylamide monomeris used. The amount of the hydrophilic methacrylamide monomer is aboutbetween 1 and about 50 weight %, in one embodiment between about 1 andabout 30 weight %, and in another embodiment between about 1 and about15 weight %, based on the monomer and polymer component in the monomermixture. An example of a hydrophilic methacrylamide monomer includeN-hydroxymethylmethacrylamide, N-(2-hydroxyethyl)methacrylamide,N-(2-hydroxypropyl)methacrylamide, N-(3-hydroxypropyl)methacrylamide,N-(2-hydroxybutyl)methacrylamide, N-(3-hydroxybutyl)methacrylamide,N-(4-hydroxy butyl)methacrylamide,N-(2-hydroxymethylphenyl)methacrylamide,N-(3-hydroxymethylphenyl)methacrylamide,N-(4-hydroxymethylphenyl)methacrylamide and the like. These alkyl andaryl groups can be straight or branched. Of these, monomers,N-(2-hydroxyethyl)methacrylamide monomer is preferable from aperspective of increasing the transparency of the polymer obtained.

In one embodiment the monomer mixture for obtaining the polymer of thepresent invention additionally contains between about 1 and about 30% ofa hydrophilic polymer with a molecular weight of about 1000 or higher inthe monomer and polymer component of the monomer mixture in order toenhance wettability, resistance to adhesion of proteins, resistance toadhesion of lipids and combinations thereof.

Examples of hydrophilic polymers that are used in the polymer of thepresent invention include poly-N-vinyl pyrrolidone,poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactum,poly-N-vinyl-3-methyl-2-caprolactum, poly-N-vinyl-3-methyl-2-piperidone,poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-caprolactum,poly-N-vinyl-3-ethyl-2-pyrrolidone,poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinyl imidazole,poly-N-vinyl formamide, poly-N-vinyl acetamide, poly-N-methyl-N-vinylacetamide, poly-N,N-dimethyl acrylamide, poly-N,N-diethyl acrylamide,poly-N-isopropyl acrylamide, polyvinyl alcohol, polyacrylate,polyethylene oxide, poly-2-ethyl oxazoline, heparine, polysaccharide,poly-acryloyl morpholine, and mixtures and copolymers thereof. Thehydrophilic polymers selected from, polyvinylpyrrolidone,poly-N,N-dimethyl acrylamide, polyacrylic acid, polyvinyl alcohol, andmixtures and copolymers thereof may be particularly effective atenhancing the wettability of certain silicone hydrogels.Polyvinylpyrrolidone and poly-N,N-dimethyl acrylamide provide a balancebetween the wet ability and the compatibility to the polymerization mixin certain formulations. Examples of suitable wetting agents aredisclosed in US2006-0072069A1, U.S. Pat. No. 6,367,929 andUS-2008-0045612A1.

If the amount of hydrophilic polymer that is used in the siliconehydrogel related to the present invention is too low, the desiredwettability may not be achieved, but if too high, the hydrophilicpolymer may not easily dissolve in the polymerization base liquid, andtherefore the amount is between about 1 and about 30 weight %, betweenabout 2 and about 25 weight %, and between about 3 and about 20 weight %of the monomer and polymer component in the polymerization mixture.Lower limit values include about 1 weight %, about 2 weight %,preferably about 3 weight %, and about 6 weight %. Upper limit valuesinclude about 30 weight %, about 25 weight %, about 20 weight %, about 9weight %. Any of the lower limit values and any of the upper limitvalues can be combined together.

If a range of the molecular weight of the hydrophilic polymer that isused in the silicone hydrogel of the present invention is too low,desirable wettability may not be provided, but if too high, thesolubility in the polymerization mixture may be inferior, and viscosityof the polymerization mixture will be increased. In one embodiment, themolecular weight is between about 1000 Daltons and about 10 millionDaltons, in other embodiments between about 100,000 Daltons and about 1million Daltons, and in other embodiments between about 200,000 Daltonsand about 800,000 Daltons. In embodiments where the hydrophilic polymercomprises at least one reactive group capable of covalently bonding withthe silicone hydrogel matrix, the molecular weight may be at least about2000 Daltons, at least about 5,000 Daltons; and in some embodimentsbetween about 5,000 to about 180,000 Daltons, or between about 5,000Daltons to about 150,000 Daltons. Lower limit values include about 1000Daltons, more about 100,000 Daltons, and about 200,000 Daltons. Upperlimit values include about 10 million Daltons, about 1 million, andabout 800,000 Daltons. Any of the preferred lower limit values and anyof the preferred upper limit values can be combined together. Themolecular weight of the hydrophilic polymer of the present invention isexpressed by the weighted average molecular weight (Mw) measured by gelpermeation chromatography (column: TSK gel GMPWXL manufactured by TosohCorporation, mobility phase: water/methanol=50/50, 0.1 N lithium nitrateadded, flow rate: 0.5 mL/minute, detector: differential refractive indexdetector, molecular weight standard sample: polyethylene glycol).

Of the monomer components used for polymerizing the polymer of thepresent invention, if the acrylamide monomer content is too low, theoverall polymerization rate will be decreased, so the amount of allacrylamide monomers is in some embodiments about 90 weight % or higher,about 95 weight % or higher, and in some embodiments about 99 weight %or higher.

The polymer of the present invention can include a monomer with two ormore reactive groups as a copolymerization component. In this case, thepolymer of the present convention is made to be solvent resistant.Preferable examples of monomers with two or more polymeric groupsinclude bifunctional and polyfunctional acrylates such as ethyleneglycol (meth)acrylate, diethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,tetraethylene glycol di(meth)acrylate, glyceryl tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, and trimethylol propane tri(meth)acrylate, and bisacrylamides such as N,N′-methylene bisacrylamide,N,N′-ethylene bisacrylamide, N,N′-propylene bisacrylamide, and the like.Of these, the bisacrylamides are preferable from a perspective ofincreased polymerization rate, and of these, N,N′-methylenebisacrylamide and N,N′-ethylene bisacrylamide are preferable. A rangefor the amount of monomer containing two or more polymeric groups thatis used is between about 0.1 and about 10 weight %, in some embodimentsbetween about 0.5 and about 8 weight %, and between about 0.8 and about5 weight %, because a favorable lens shape can be obtained. Lower limitvalues include about 0.1 weight %, about 0.5 weight %, and about 0.8weight %. Upper limit values include about 10 weight %, about 8 weight%, and about 5 weight %. Any of the preferred lower limit values and anyof the preferred upper limit values can be combined together.

When obtaining the polymer of the present invention by polymerization apolymerization initiator may also be added to enhance polymerization.Suitable initiators include, thermal polymerization initiators such as aperoxide compound or an azo compound, or photopolymerization initiators.In some embodiments, photoinitiators are added in order to enhancepolymerization. If thermal polymerization is used, a thermalpolymerization initiator that has optimal decomposition properties atthe desired reaction temperature is selected and used. Generally, an azotype initiator or a peroxide type initiator where the 10 hour half-lifetemperature is between about 40° C. and about 120° C. is preferable.Examples of photopolymerization initiators include carbonyl compounds,peroxide compounds, azo compounds, sulfur compounds, halogenatedcompounds, metal salts, and the like. More specific examples ofphotoinitiators include as aromatic alpha-hydroxy ketones,alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphineoxides, and a tertiary amine plus a diketone, mixtures thereof and thelike. Illustrative examples of photoinitiators are 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one,bis(2,6-dimethoxybenzoyl)-2, 4-4-trimethylpentyl phosphine oxide(DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenyl phosphineoxide (Irgacure819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide and2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ether anda combination of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.Commercially available visible light initiator systems include Irgacure819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850 (all fromBASF) and Lucirin TPO initiator (available from BASF). Commerciallyavailable UV photoinitiators include Darocur 1173 and Darocur 2959(BASF). These and other photoinitiators which may be used are disclosedin Volume III, Photoinitiators for Free Radical Cationic & AnionicPhotopolymerization, 2^(nd) Edition by J. V. Crivello & K. Dietliker;edited by G. Bradley; John Wiley and Sons; New York; 1998, which isincorporated herein by reference. These polymerization initiators can beused independently or blended together, and the amount used isapproximately 1 weight % for 100 weight % of monomer component.

Other components that can be present in the reaction mixture used toform the contact lenses of this invention include, ultra-violetabsorbing compounds, medicinal compounds, nutraceutical compounds,antimicrobial compounds, copolymerizable and nonpolymerizable dyes,including dyes and compounds which reversibly change color or reflectlight when exposed to various wavelengths of light, release agents,reactive tints, pigments, combinations thereof and the like.

When obtaining the polymer of the present invention by polymerization, apolymerization solvent can be used. The solvent can be any type oforganic or inorganic solvent. Solvents useful in preparing the devicesof this invention include ethers, esters, alkanes, alkyl halides,silanes and alcohols. Examples of ethers useful as diluents for thisinvention include tetrahydrofuran. Examples of esters useful for thisinvention include ethyl acetate. Examples of alkyl halides useful asdiluents for this invention include methylene chloride. Examples ofsilanes useful as diluents for this invention includeoctamethylcyclotetrasiloxane. Examples of alcohols useful as diluentsfor this invention include hexanol, heptanol, octanol, nonanol, decanol,tert-butyl alcohol, 3-methyl-3-pentanol, isopropanol, and3,7-dimethyl-3-octanol. Additional diluents useful for this inventionare disclosed in U.S. Pat. No. 6,020,445, which is incorporated hereinby reference.

Examples that can be used include water, methanol, ethanol, propanol,2-propanol, butanol, tert-butanol, tert-amyl alcohol,3,7-dimethyl-3-octanol, tetrahydrolinalool, and other alcohol typesolvents; benzene, toluene, xylene, and other types of aromatichydrocarbon solvents; hexane, heptane, octane, decane, petroleum ether,kerosene, ligroin, paraffin, and other types of aliphatic hydrocarbonsolvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, andother ketone type solvents; ethyl acetate, butyl acetate, methylbenzoate, ethylene glycol diacetate, and other ester type solvents;diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkyl ether,diethylene glycol dialkyl ether, triethylene glycol dialkyl ether,tetraethyleneglycol dialkyl ether, polyethylene glycol dialkyl ether,polyethylene glycol-poly propylene glycol block copolymer, polyethyleneglycol-poly propylene glycol random copolymer, and other types of glycolether solvents. The solvents can be used individually or combined. Ofthese, alcohol type solvents and glycol ether type solvents arepreferable from a perspective that the solvents can easily be removedfrom the polymer obtained by washing with water.

The polymer of the present invention can be used independently bymolding into the desired shape, but can also be blended with othermaterials and then molded. Furthermore, a coating is preferably appliedto the surface of the molded parts.

Applications for the polymer of the present invention include ophthalmiclenses, endoscopes, catheters, transfusion tubes, gas transport tubes,stents, sheaths, cuffs, tube connectors, access ports, drainage bags,blood circuits, wound covering material, and various types of medicinecarriers, but contact lenses, intraocular lenses, artificial cornea,cornea inlays, and cornea onlays are particularly suitable, and contactlenses are most suitable.

When the polymer of the present invention is molded and used as anophthalmic lens, the polymerization method and molding method can bestandard methods as follows. Examples include a method of first moldingthe silicone hydrogel into a round bar or plate and then machining tothe desired shape by a cutting process or the like, a moldpolymerization method, a spin cast method, and the like.

As one example, the case where an ophthalmic lens is made from thepolymer of the present invention using a mold polymerization method isdescribed next.

A monomer composition is injected into the space between two molds whichhave a lens shape. Next, photopolymerization or thermal polymerizationis performed to form the lens shape. The mold is made from plastic,glass, ceramic, metal, or the like, but for the case of photopolymerization, an optically transparent material is used, and normallyplastic or glass is used. When manufacturing the polymer, a space isformed by two counterfacing molds, and the monomer composition isinjected into the space. Next, the mold with the space filled with themonomer composition is irradiated with an activating light such asultraviolet light, visible light or a combination thereof, or placed inan oven or bath and heated to polymerize the monomer. It is alsopossible to use both methods, by thermal polymerization afterphotopolymerization or conversely by using photopolymerization afterthermal polymerization. For the case of photopolymerization, generally alight containing a high level of light from a light source, such as amercury lamp or a fluorescent lamp for example, is irradiated for ashort period of time (normally 1 hour or less). When performing thermalpolymerization, conditions where the temperature is gradually increasedfrom near room temperature to a high temperature of between about 60° C.and about 200° C. over the course of several hours to several tens ofhours is preferable in order to maintain the optical consistency andquality of the polymer and to increase the reproducibility.

The polymer of the present invention can optionally be modified byvarious methods. If the application is an ophthalmic lens, and ahydrophilic polymer is not internally included, a modification processmay be performed in order to improve the wetting properties of the lens.

Specific modification methods include electromagnetic (including light)irradiation, plasma irradiation, vapor deposition, chemical vapordeposition treatment such as sputtering, heating, mold transfer coating,charge association coatings, base treatments, acid treatments, andtreatments with other suitable surface treatment agents, andcombinations thereof can also be used. Of these modification means, basetreatments and acid treatments are preferable because they are simple.

Examples of a base treatment or acid treatment include a method ofbringing a molded part into contact with a basic or acidic solution, ora method of bringing a molded part into contact with a basic or acidicgas. More specific methods include, for example, a method of immersing amolded parts in a basic or acidic solution, a method of spraying a basicor acidic solution or a basic or acidic gas onto a molded parts, amethod of applying a basic or acidic solution onto a molded part using apaddle or brush or the like, a method of spin coating a basic or acidicsolution onto a molded part, a dip coat method, and the like. Thesimplest method that provides a large modification affect is a method ofimmersing a molded part in a basic or acidic solution.

A temperature range when immersing the polymer in a basic or acidicsolution is not particularly restricted, but normally the temperature iswithin a range between approximately about −50° C. and about 300° C.When considering an ease of work, a temperature range between about −10°C. and about 150° C. is more preferable, and a range between about −5°C. and about 60° C. is most preferable. A lower limit value ispreferably about −50° C., more preferably about −10° C., and even morepreferably -about 5° C. An upper limit value is preferably about 300°C., more preferably about 150° C., and even more preferably about 60° C.Any of the preferred lower limit values and any of the preferred upperlimit values can be combined together.

The optimum time that the polymer is immersed in the basic or acidicsolution varies depending on the temperature, but generally 100 hours orless is preferable, 24 hours or less is more preferable, and 12 hours orless is most preferable. If the contact time is too long, not only willthe ease of work and the productivity be inferior, but there may also benegative effects such as reducing the oxygen permeability and degradingthe mechanical properties.

Examples of bases that can be used include alkali metal hydroxides,alkali earth metal hydroxides, various types of carbonates, varioustypes of borates, various types of phosphates, ammonia, various ammoniumsalts, various amines, and polymer bases such as polyethyleneimine andpolyvinyl amine and the like. Of these, alkali metal hydroxides are mostpreferable because of the low cost and the strong treatment effect.

Examples of acids that can be used include various types of inorganicacids such as sulfuric acid, phosphoric acid, hydrochloric acid, andnitric acid; various types of organic acids such as acetic acid, formicacid, benzoic acid, and phenol; and various types of polymer acids suchas polyacrylic acid and polystyrene sulfonic acid and the like. Ofthese, polymer acids are most preferable because the treatment effect isstrong and the negative effect on other physical properties is minimal.

The solvent for the basic or acidic solution can be any type ofinorganic or organic solvent. Examples include water, methanol, ethanol,propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol,triethylene glycol, tetraethyleneglycol, polyethylene glycol, glycerin,and other alcohols, benzene, toluene, xylene, and other aromatichydrocarbons, hexane, heptane, octane, decane, petroleum ether,kerosene, ligroin, paraffin, and other aliphatic hydrocarbons, acetone,methyl ethyl ketone, methyl isobutyl ketone, and other ketones, ethylacetate, butyl acetate, methyl benzoate, dioctyl phthalate, and otheresters, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkylether, diethyl glycol dialkyl ether, triethylene glycol dialkyl ether,tetraethyleneglycol dialkyl ether, polyethylene glycol dialkyl ether andother ethers; dimethylformamide, dimethyl acetoamide,N-methyl-2-pyrrolidone, dimethyl imidazolidinone, hexamethyl phospholictriamide, dimethyl sulfoxide and other non-protonic polar solvents,methylene chloride, chloroform, dichloroethane, trichloroethane,trichloroethylene, other halogen type solvents, freon type solvents, andthe like. Of these, water is most preferable from the perspective ofeconomics, simplicity of handling, and chemical stability and the like.The solvent can also be a blend of two or more types.

With the present invention, the basic or acidic solution that is usedmay contain components other than the basic or acidic substance and thesolvent. The basic or acidic substance can be removed from the polymerby washing after the basic or acidic treatment.

The washing solvent can be any type of inorganic or organic solvent.Examples include water, methanol, ethanol, propanol, 2-propanol,butanol, ethylene glycol, diethylene glycol, triethylene glycol,tetraethyleneglycol, polyethylene glycol, glycerin, and other alcohols,benzene, toluene, xylene, and other aromatic hydrocarbons, hexane,heptane, octane, decane, petroleum ether, kerosene, ligroin, paraffin,and other aliphatic hydrocarbons, acetone, methyl ethyl ketone, methylisobutyl ketone, and other ketones, ethyl acetate, butyl acetate, methylbenzoate, dioctyl phthalate, and other esters, diethyl ether,tetrahydrofuran, dioxane, ethylene glycol dialkyl ether, diethyleneglycol dialkyl ether, triethylene glycol dialkyl ether, tetraethyleneglycol dialkyl ether, polyethylene glycol dialkyl ether and otherethers; dimethylformamide, dimethyl acetoamide, N-methyl-2-pyrrolidone,dimethyl imidazolidinone, hexamethyl phospholic triamide, dimethylsulfoxide and other non-protonic polar solvents, methylene chloride,chloroform, dichloroethane, trichloroethane, trichloroethylene, otherhalogen type solvents, and freon type solvents.

The washing solvent can be a blend of two or more types. The washingsolvent can contain components other than solvent, such as inorganicsalts, surfactants, and cleaning agents.

Modification treatment as described above can be performed on the entirepolymer or can be performed only on a portion of the polymer such asonly on the surface. If the modifications are performed only on thesurface, the surface wet ability alone can be enhanced withoutdramatically changing the physical properties of the entire polymer.

If a water content range of the polymer of the present invention is toolow, the silicone hydrogel will be hard, but if the water content is toohigh, water may evaporate from the surface of the silicone hydrogel andthe wearer may a dry lens feeling during lens wear, so water contentbetween about 20 and about 50 weight % are desirable, between about 25and about 45 weight % is more preferable, and between about 30 and about40 weight % is most preferable. Lower limit values include about 20weight %, about 25 weight %, and about 30 weight %. Upper limit valuesare about 50 weight %, about 45 weight %, and about 40 weight %. Any ofthe preferred lower limit values and any of the preferred upper limitvalues can be combined together.

An elastic modulus of the polymer of the present invention is about 200psi or less, in some embodiments less than about 150 psi or less, and inother embodiments less than about 100 psi or less, in order to obtaincomfortable feel when being worn when the use is an ophthalmic lens andparticularly a soft contact lens.

An elongation of the polymer of the present invention is about 100% orhigher, in some embodiments about 150% or higher, and in otherembodiments about 200% or higher. Higher elongation values mean that thesilicone hydrogel will not easily break. The elastic modulus andelongation of the polymer of the present invention are measured bycutting out an array shape sample where a width of the narrowest sectionis 5 mm, and then stretching at a rate of 100 mm/minute using a tensiletester.

An advancing contact angle of the polymer of the present invention isabout 70 degrees or less, about 60 degrees or less, and in someembodiments about 50 degrees or less, if the application is anophthalmic lens. The advancing contact angle of the polymer of thepresent invention is obtained by measuring a short strip sample with awidth of 5 mm cut from a lens shaped sample, at an immersion rate of 7mm/minutes using a dynamic contact angle meter.

As for the oxygen permeability of the polymer of the present invention,the oxygen permeability constant is desirably 50×10⁻¹¹ (cm²/sec) mLO₂/(mL-hPa) or higher and in some embodiments 50×10⁻¹¹(cm²/sec)mLO₂/(mL·hPa) or higher. The oxygen permeability constant ofthe polymer of the present invention is a value measured by apolarographic method.

As for the transparency of the polymer of the present invention, thewhole light transmissivity is desirably about 85% or higher, about 88%or higher, and about 91% or higher when the application is an ophthalmiclens. The whole light transmissivity of the polymer of the presentinvention is obtained by lightly wiping the water from a lens shapedsample with a thickness between 0.14 and 0.15 mm, setting the sample inthe light path of a light transmissivity measuring apparatus, and thenmeasuring the whole light transmissivity.

A value that expresses the shape recovery properties of the polymer ofthe present invention is a stress zero time measured by a measurementmethod described later. A shorter stress zero time indicates that theshape recovery properties of the silicone hydrogel are favorable, and avalue of 1 second or less is desirable, 0.95 seconds or less is morepreferable, and 0.9 seconds or less is most preferable. Measurement ofthe stress zero time of the polymer of the present invention isperformed by the following method. A 5 mm wide 1.5 cm long strip samplewas cut from near the center of a lens, and measured using a dynamicviscoelasticity measuring device. The sample was mounted at a chuckwidth of 5 mm, and after stretching 5 mm at a rate of 100 mm/minute,this sample was returned to the original length (5 mm) at the same rate,and this cycle was repeated 3 times. From the moment that the stressbecame zero part way through returning the sample to the original lengththe second time, the length of time until the moment that stress beganto be applied (stress was no longer zero) after beginning the thirdstretch cycle was determined to be the stress zero time.

The polymer obtained by polymerizing the silicone monomer of the presentinvention is suitable for various medical implements such as ophthalmiclenses, endoscopes, catheters, transfusion tubes, gas transport tubes,stents, sheaths, cuffs, tube connectors, access ports, drainage [bags],blood circuits, wound covering material, and various types of medicinecarriers, but is particularly suitable for contact lenses, intraocularlenses, and artificial corneas.

The present invention will be described in further detail below throughthe use of working examples, but the present invention is not limited tothese working examples.

Measurement Method

(1) GC Measurement

Device

Shimadzu GC-18A (FID detector)

Capillary column

Agilent HP-ULTRA2 (length 25 m×inner diameter 0.32 mm×film thickness0.52 micrometers)

Temperature program

Injection port temperature: 300° C.

Detector temperature: 320° C.

Column temperature: Initial temperature 50° C. (1 minute)→increasedtemperature at rate of 10° C./minute→300° C. (maintain for 14 minutes)(total 40 minutes)

Carrier gas

Helium gas (110 kPa)

Sample Preparation

100 μL of reaction solution diluted with 1 mL of solvent (toluene,2-propanol, or ethyl acetate) was used as the sample.

(2) Whole Light Transmissivity

The whole light transmissivity was measured using an SM color computer(model SM-7-CH, manufactured by Suga Test Instruments Co. Ltd.). Wateron the lens sample is lightly wiped off, and then the sample is set inthe light path and measured. The thickness was measured using an ABCDigimatic Indicator (ID-C112, manufactured by Mitsutoyo Corporation),and samples with a thickness between 0.14 and 0.15 mm were measured.

(3) Elastic Modulus and Elongation

An array shaped sample with a width of 5 mm in the narrowest region wascut from the lens sample, the thickness was measured using an ABCDigimatic Indicator (ID-C112, manufactured by Mitsutoyo 100 mm/minute,and then the elastic modulus and the elongation were measured using aTensilon (RTM-100 manufactured by Toyo Baldwin Co. Ltd., cross headspeed 100 mm/minute).

(4) Water Content

The weight of the silicone hydrogel when containing water (W1) and theweight when dry (W2) were measured and the water content was calculatedfrom the following formula.Water content (%)=(W1−W2)/W1×100

However, with the present invention, the condition where the siliconehydrogel contains water refers to a condition where the siliconehydrogel has been immersed in saline solution water at 25° C. for 6hours or longer. Furthermore, a dry condition for the silicone hydrogelrefers to a condition where drying has been performed for 16 hours orlonger in a vacuum dryer at 40° C.

(5) Advancing Contact Angle

A short strip sample with a width of 5 mm was cut from the lens sample,and the dynamic contact angle was measured (advancing and receding)using a WET-6000 dynamic contact angle meter manufactured by RhescaCorporation (immersion rate 7 mm/minute). After obtaining themeasurement value, the value for the advancing contact angle was used asan indicator of the wettability.

(6) Stress Zero Time

A 5 mm wide 1.5 cm long strip sample was cut from near the center of alens, and measured using a CR-500DX rheometer manufactured by SunScientific Co. Ltd. The sample was mounted at a chuck width of 5 mm, andafter stretching 5 mm at a rate of 100 mm/minute, this sample wasreturned to the original length (5 mm) at the same rate, and this cyclewas repeated 3 times. From the moment that the stress became zero partway through returning the sample to the original length the second time,the length of time until the moment that stress began to be applied(stress was no longer zero) after beginning the third stretch cycle wasdetermined to be the stress zero time.

(7) Conversion by DSC

Thermal analysis of the cure of a reactive monomer mix (RMM) was carriedout using photo-differential scanning calorimetry (photo-DSC). A sampleof ˜10 mg of the RMM under consideration was weighed into a DSC pan andplaced, along with an empty reference pan, onto the stage of a Q100 DSCfrom TA Instruments. The sample chamber was purged with dry nitrogen (50mL/min) during the analysis. The sample was heated to 70° C., an LEDlight source (˜420 nm, 4.0 mW/cm²) was triggered to activate thephotoinitiator and the heat evolved (enthalpy, J/g) during isothermalcure for 10 minutes was measured. The total enthalpy was derived fromintegration of the area of the DSC trace of enthalpy over time and thepercent conversion at various time points was calculated.

Synthesis Example 1

28 to 30 weight percent ammonia water (320 mL) and methanol (48 mL) wereplaced in a 500 mL 4-necked flask, and a mechanical stirrer, droppingfunnel, reflux condenser, and glass stopper were attached. A solution ofallyl glycidyl ether (59.6 g, 0.522 mol)/methanol (48 mL) was addeddropwise into the flask over the course of approximately 9 hours whilemaintaining the 4-necked flask at a temperature of approximately 25° C.using a circulator. Completion of the reaction was confirmed using GC.

After the reaction was complete, the reaction solution was concentratedin an evaporator. The liquid obtained was purified using distillationunder reduced pressure (full vac., 81° C.). The yield was 31.6 g (46.1%yield) and the GC purity was 99.0%.

Synthesis Example 2

The compound obtained in synthesis example 1 (30.0 g, 0.229 mol),hexamethyldisilazane (22.2 g, 0.137 mol), BHT (0.09 g), and saccharine(0.09 g) were placed in a 200 mL 4-necked flask and mixed for 2 hours at100° C.

The reaction was ended after confirming the elimination of the rawmaterial peaks using GC measurement. After purifying by distillationunder reduced pressure (full vac., 72° C.), the yield was 39.0 g (yieldrate 83.9%), and the GC purity was 99.4%.

Synthesis Example 3

The compound obtained by synthesis example 2 (38.0 g, 0.187 mol),1-n-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane expressed by thefollowing formula

(hereinafter referred to as “SiL5B”) (77.2 g, 0.187 mol), a 0.104 Mmethylvinyl cyclosiloxane solution of platinum (0)2,4,6,8-tetramethyl-2.4.6.8-tetravinyl cyclotetrasiloxane complex(manufactured by Aldrich Corp., hereinafter referred to as “platinumtetra solution”) (610 μL, and toluene (370 μL) were placed in a 200 mL4-necked flask, and then heated to 120° C. and mixed.

After 2 hours, an additional 610 μL of platinum tetra solution was addedbecause raw material was found to be remaining by the GC measurement,and the reaction was continued for another hour. After confirmingelimination of the raw materials by GC, the solution was cool to roomtemperature and concentrated in an evaporator. The liquid obtained waspurified by distillation under reduced pressure (8×10⁻² Pa, 156° C.)using an oil diffusion pump. The yield was 65.5 g (56.9% yield), and theGC purity was 95.0%.

Synthesis Example 4

The compound obtained by synthesis example 3 (64.0 g, 0.104 mol),triethylamine (10.5 g, 0.104 mol) and hexane (170 mL) were placed in a500 mL 4-necked flask, acryloyl chloride (9.40 g, 0.104 mol) and hexane(130 mL) were added by drops using a dropping funnel over a period ofapproximately 6 hours while in an ice bath (−1 to 2° C.). 40 minutesafter dropwise addition was complete, A GC measurement was performed andit was confirmed that nearly all of the raw materials were exhausted.

One hour after the start of dropwise addition, the reaction solution wasfiltered and the precipitate was washed with hexane that had been cooledin a refrigerator. The wash solution was combined with the filtrate,transferred to a separation funnel, and washed three times with water(300 mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (300 mL) and two times with a saturated aqueous solution ofsodium chloride (300 mL).

The organic layer was dried overnight using sodium sulfate, filtered,and then concentrated using an evaporator. The yield of the crudematerial obtained was 58.7 g (84.3% crude yield).

Working Example 1

The crude product obtained by Synthesis Example 4 (57.0 g, 0.085 mol),methanol (171 g), and acetic acid (28.5 g) were placed in a 300 mLeggplant flask and mixed for approximately 1 hour at 40° C.

Exhaustion of raw materials was confirmed using TLC, and afterconcentrating in an evaporator, 350 mL of hexane was added, and thesolution was transferred to a separation funnel. The solution was washedtwo times each with water (250 mL), a saturated aqueous solution ofsodium hydrogen carbonate (250 mL), and a saturated aqueous solution ofsodium chloride (250 mL). The organic layer was dried overnight usingsodium sulfate, filtered, and then concentrated using an evaporator. Theyield of the crude material was 50.83 g.

23.63 g of the crude material was purified in a column. The weight ofsilica gel used was approximately 5 times (120 g) the weight of thecrude material. Elution was performed by TLC using hexane/ethylacetate=1/1 until the target spot was eliminated. Several fractions weremeasured by a GC at both ends of the recovery range and the range of thefractions where all by product peaks were less than 1% were measured andcollected. 6.0 mg of BHT and 2.0 mg of MEHQ were added and concentrated,and then the pressure was reduced using a vacuum pump while mixing foran additional 1 hour at 60° C. to remove the residual solvent. It wasconfirmed that a solvent peak was not observed using NMR. The yield was20.14 g (85.2% yield), and the GC purity was 95.2%.

Synthesis Example 5

Allylamine (112.4 mL, 85.54 g, 1.5 mol) was placed in a 4-necked flaskand a reflex condenser, thermometer, dropping funnel, and mechanicalstirrer were attached. Glycidol (2,3-epoxy-1-propanol, 37.8 g, 0.5 mol)was added to the dropping funnel, and added by drops over approximately10 minutes while mixing at 30° C. A GC measurement was performed eachhour starting at the time that dropwise addition was completed in orderto confirm the progress of the reaction. 5 hours after dropwise additionwas completed it was confirmed that the glycidol peak was 1% or less andthe reaction was terminated. The solution was concentrated in anevaporator, and then purified by reduced pressure installation (fullvac, by 52° C.). The yield was 27.43 g (41.8% yield), and the GC puritywas 98.7%.

Synthesis Example 6

The compound obtained in synthesis example 5 (23.2 g, 0.177 mol),hexamethyldisilazane (33.89 g, 0.210 mol), BHT (72 mg), and saccharine(70 mg) were placed in a 4-necked flask and a reflex condenser,thermometer, and mechanical stirrer were attached. The reaction wasperformed for 2 hours at 100° C. and the reaction was terminated afterconfirming that the reactants were reduced or exhausted using GC. Thereaction solution was concentrated in an evaporator, and then purifiedby distillation under reduced pressure (full vac, by 77° C.). The yieldwas 36.31 g (70.2% yield), and the GC purity was 98.4%.

Synthesis Example 7

The compound obtained by synthesis example 6 (35.0 g, 0.127 mol), SiL5B(52.4 g, 0.127 mol), toluene (263 mL), and platinum tetra solution (350μL) were placed in a 1 L 3-necked flask and a reflex condenser,thermometer, and mechanical stirrer were attached. The reaction wasperformed at 120° C. while making GC measurements each hour. Anadditional 350 μL of platinum tetra solution was added because rawmaterial was remaining after 4 hours. The solution was heated andstirred for an additional 4 hours and then the reaction was terminated.The reaction solution was concentrated in an evaporator, and thenpurified by distillation under reduced pressure (8×10⁻² Pa, 176° C.).The yield was 58.22 g (66.6% yield) and the GC purity was 96.2%.

Synthesis Example 8

The compound obtained by synthesis example 7 (55 g, 0.080 mol),triethylamine (8.08 g, 0.080 mol), and ethyl acetate (130 mL) wereplaced in a 1 L 3-necked flask and a dropping funnel, thermometer, andmechanical stirrer were attached. Acryloyl chloride (7.23 g, 0.080 mol)and ethyl acetate (100 mL) were placed in the dropping funnel. The3-necked flask was placed in an ice bath containing salt and dropwiseaddition was started after waiting for the internal temperature to dropto 0° C. While maintaining the internal temperature between −2 and 3°C., dropwise addition was performed over approximately 3 hours and afterdropwise addition was completed, the reaction was continued for anotherhour and then terminated. The solution was then filtered while washingwith a small amount of chilled ethyl acetate that had been chilled in arefrigerator. The filtrate was transferred to a separation funnel and400 mL off hexane was added. The solution was washed two times withwater (200 mL), two times with a saturated aqueous solution of sodiumhydrogen carbonate (200 mL), and two times with a saturated aqueoussolution of sodium chloride (200 mL). Anhydrous sodium sulfate was addedto the organic layer and drying was performed overnight. Afterfiltering, this solution was concentrated in an evaporator to obtaincrude product. The crude yield was 54.6 g and the GC purity was 88.5%.

Working Example 2

The crude product obtained by synthesis example 8 (54.6 g, 0.074 mol), 3parts (weight ratio) of methanol (163.8 g) and one half part (weightratio) of acetic acid (27.3 g) was added for each part of crude product,and then the solution was mixed for 1 hour at 40° C. After reacting, thesolution was concentrated in an evaporator.

The liquid obtained (70.5 g) was transferred to a separation funnel, and4 parts of hexane (volumetric ratio) (280 g) were added to one part ofliquid. The solution was washed two times each with water (210 mL), asaturated aqueous solution of sodium hydrogen carbonate (200 mL), and asaturated aqueous solution of sodium chloride (250 mL), and then theorganic layer was dried overnight using anhydrous sodium sulfate. Thesolution was concentrated in an evaporator to obtain 35.03 g of crudematerial. 35 g of the crude material was purified in a column. Theamount of silica gel used was five times the weight of the crudematerial (175 g). For the solvent, hexane/ethyl acetate=5/1 was useduntil impurities were discharged (2.48 L), and after confirming that theimpurities had been discharged, the target material was eluted usinghexane/ethyl acetate=1/3 (1.6 L). The range of the fraction containingthe target material was confirmed using TLC, and several fractions onboth ends of this range were measured by GC, and only fractions wherethe byproducts were less than 1% were collected. 6.0 mg of BHT and 2.0mg of MEHQ were added and the solution was concentrated in anevaporator. The solution was stirred at 60° C. while reducing thepressure using a vacuum pump for 1 hour in order to remove the remainingsolvent, and it was confirmed that a residual solvent peak was notobserved using NMR. The yield was 18.69 g (43% yield) and the GC puritywas 95.2%.

Synthesis Example 9

40 weight % methylamine in water (233 g, 3.0 mol) and methanol (35 mL)were placed in a 500 mL 4-necked flask, and a mechanical stirrer,dropping funnel, reflux condenser, and glass stopper were attached. Asolution of allyl glycidyl ether (34.2 g, 0.3 mol)/methanol (35 mL) wasadded dropwise into the flask over the course of approximately 5 hourswhile maintaining the 4-necked flask at a temperature of approximately25° C. using a circulator. Completion of the reaction was confirmedusing GC.

After the reaction was complete, the reaction solution was concentratedin an evaporator. The liquid obtained was purified using distillationunder reduced pressure (full vac., 76° C.). The yield was 35.3 g (81%yield) and the GC purity was 99.2%.

Synthesis Example 10

The compound obtained in Synthesis Example 9 (16.6 g, 0.114 mol),hexamethyldisilazane (11.2 g, 0.069 mol), BHT (0.05 g), and saccharine(0.05 g) were placed in a 100 mL 3-necked flask and mixed for 3 hours at100° C.

The reaction was ended after confirming the elimination of the rawmaterial peaks using GC measurement. After purifying by distillationunder reduced pressure (full vac., 68° C.), the yield was 22.31 g (90%yield), and the GC purity was 99%.

Synthesis Example 11

The compound obtained by Synthesis Example 10 (5.0 g, 0.023 mol), SiL5B(9.50 g, 0.023 mol), toluene (46 mL), and platinum tetra solution (80μL) were placed in a 300 mL 3-necked flask and a reflux condenser,thermometer, and mechanical stirrer were attached. The reaction wasperformed at 50° C. for 1.5 hours. The reaction solution wasconcentrated in an evaporator, and then purified by distillation underreduced pressure (0.02 mmHg, 135° C.). The yield was 8.3 g (57% yield)and the GC purity was 93%.

Synthesis Example 12

The compound obtained by Synthesis Example 11 (20.0 g, 0.032 mol),triethylamine (3.21 g, 0.032 mol) and hexane (54 mL) were placed in a200 mL 3-necked flask, acryloyl chloride (3.1 mL, 0.038 mol) and hexane(32 mL) were added by drops using a dropping funnel over a period ofapproximately 2 hours while in an ice bath (−10 to −5° C.). 40 minutesafter dropwise addition was complete, A GC measurement was performed andit was confirmed that nearly all of the raw materials were exhausted.

One hour after the start of dropwise addition, the reaction solution wasfiltered and the precipitate was washed with hexane that had been cooledin a refrigerator. The wash solution was combined with the filtrate,transferred to a separation funnel, and washed three times with water(50 mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (50 mL) and two times with a saturated aqueous solution ofsodium chloride (50 mL).

The organic layer was dried overnight using sodium sulfate, filtered,and then concentrated using an evaporator. The yield of the crudematerial obtained was 21.6 g (94% crude yield).

Working Example 3

The crude product obtained by Synthesis Example 12 (12.0 g, 0.017 mol),methanol (36 g), and acetic acid (5 mL) were placed in a 100 mL eggplantflask and mixed for approximately 1 hour at 40° C.

Exhaustion of raw materials was confirmed using TLC, and afterconcentrating in an evaporator, 50 mL of hexane was added, and thesolution was transferred to a separation funnel. The solution was washedtwo times each with water (40 mL), a saturated aqueous solution ofsodium hydrogen carbonate (40 mL), and a saturated aqueous solution ofsodium chloride (40 mL). The organic layer was dried overnight usingsodium sulfate, filtered, and then concentrated using an evaporator. Theyield of the crude material was 11.1 g.

10.00 g of the crude material was purified in a column. The weight ofsilica gel used was approximately 5 times (50 g) the weight of the crudematerial. Elution was performed by TLC using hexane/ethyl acetate=1/3until the target spot was eliminated. Several fractions were measured bya GC at both ends of the recovery range and the range of the fractionswhere all by product peaks were less than 1% were measured andcollected. 3.0 mg of BHT and 1.0 mg of MEHQ were added and concentrated,and then the pressure was reduced using a vacuum pump while mixing foran additional 1 hour at 60° C. to remove the residual solvent. It wasconfirmed that a solvent peak was not observed using NMR. The yield was11.4 g (78% yield), and the GC purity was 98%.

Synthesis Example 13

Diallylamine (2.49 mL, 0.02 mol), SiL5B (24.76 g, 0.06 mol), toluene (40mL), and platinum tetra solution (0.07 mL) were placed in a 200 mL3-necked flask and a reflux condenser, thermometer, and mechanicalstirrer were attached. The reaction was performed at 100° C. for 3hours. The reaction solution was concentrated in an evaporator, and thenlow-boiling-point impurities was distilled off under reduced pressure(0.02 mmHg, 97° C.). The yield was 14.46 g (74% yield).

Working Example 4

The compound obtained by Synthesis Example 13 (9.2 g, 0.01 mol),triethylamine (1.8 mL, 0.013 mol) and hexane (15 mL) were placed in a100 mL 3-necked flask, acryloyl chloride (1.05 mL, 0.013 mol) was addedby drops using a syringe. 40 minutes after dropwise addition wascomplete, A GC measurement was performed and it was confirmed thatnearly all of the raw materials were exhausted.

2 hours after the start of dropwise addition, the reaction solution wasfiltered and the precipitate was washed with hexane that had been cooledin a refrigerator. The wash solution was combined with the filtrate,transferred to a separation funnel, and washed three times with water(50 mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (50 mL) and two times with a saturated aqueous solution ofsodium chloride (50 mL).

The organic layer was dried overnight using sodium sulfate, filtered,and then concentrated using an evaporator. The yield of the crudematerial obtained was 9.99 g. 3.1 g of the crude material was purifiedby preparative GPC and 2.06 g of purified silicone acrylamide monomerexpressed by the following formula (s1) was obtained.

Synthesis Example 14

Allylamine (5.0 g, 87 mmol), SiL5B (39.50 g, 95.7 mmol), toluene (100mL), and platinum tetra solution (100 μL) were placed in a 300 mL4-necked flask and a reflux condenser, thermometer, and mechanicalstirrer were attached. The reaction was performed at 110° C. for 3hours. The reaction solution was concentrated in an evaporator, and thenpurified by distillation under reduced pressure (0.17 mmHg, 118° C.).The yield was 32.93 g (81% yield) and the GC purity was 96%.

Working Example 5

The compound obtained by Synthesis Example 14 (4.67 g, 0.01 mol),triethylamine (1.8 mL, 0.013 mol) and hexane (15 mL) were placed in a100 mL 3-necked flask, acryloyl chloride (1.05 mL, 0.013 mol) and hexane(32 mL) were added by drops using a syringe while in an ice bath (−10 to−5° C.). 40 minutes after dropwise addition was complete, A GCmeasurement was performed and it was confirmed that nearly all of theraw materials were exhausted.

2 hours after the start of dropwise addition, the reaction solution wasfiltered and the precipitate was washed with hexane that had been cooledin a refrigerator. The wash solution was combined with the filtrate,transferred to a separation funnel, and washed three times with water(50 mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (50 mL) and two times with a saturated aqueous solution ofsodium chloride (50 mL).

The organic layer was dried overnight using sodium sulfate, filtered,and then concentrated using an evaporator. The yield of the crudematerial obtained was 5.31 g. The crude material was purified by columnchromatography (hexane/ethyl acetate=4/1 to 2/1 as eluent, yield:31.3%).

Synthesis Example 15

N-methyl-N-allylamine (5.11 g, 71.8 mmol), SiL5B (24.7 g, 60 mmol),toluene (120 mL), and platinum tetra solution (100 μL) were placed in a300 mL 4-necked flask and a reflux condenser, thermometer, andmechanical stirrer were attached. The reaction was performed at 110° C.for 2 hours. The reaction solution was concentrated in an evaporator,and then purified by distillation under reduced pressure (0.17 mmHg,115° C.). The yield was 20.34 g (70% yield) and the GC purity was 96%.

Working Example 6

The compound obtained by Synthesis Example 15 (4.84 g, 0.01 mol),triethylamine (1.8 mL, 0.013 mol) and hexane (15 mL) were placed in a100 mL 3-necked flask, acryloyl chloride (1.05 mL, 0.013 mol) was addedby drops using a syringe while in an ice bath (−10 to −5° C.). 40minutes after dropwise addition was complete, A GC measurement wasperformed and it was confirmed that nearly all of the raw materials wereexhausted.

2 hour after the start of dropwise addition, the reaction solution wasfiltered and the precipitate was washed with hexane that had been cooledin a refrigerator. The wash solution was combined with the filtrate,transferred to a separation funnel, and washed three times with water(50 mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (50 mL) and two times with a saturated aqueous solution ofsodium chloride (50 mL).

The organic layer was dried overnight using sodium sulfate, filtered,and then concentrated using an evaporator. The yield of the crudematerial obtained was 5.45 g. The crude material was purified by columnchromatography (hexane/ethyl acetate=5/1 to 3/1 as eluent) and 1.06 g ofpurified silicone acrylamide monomer was obtained.

Working Example 7

The silicone monomer expressed by the following formula (s2)

that was obtained in working example 1 (0.925 g, 56.06 weight %),N,N-dimethyl acrylamide (0.510 g, 30.91 weight %), and the hydrophilicacrylamide monomer expressed by the following formula (h1)

(0.0 17 g, 1 weight %, polyvinyl pyrrolidone (PVP K90, 0.132 g, 8 weight%), N,N′-methylene bisacrylamide (MBA, 0.0 18 g, 1.10 weight %), UVabsorber 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole(0.0 36 g, 2.20 weight %), 3-methyl-3-pentanol (3M3P, 1.350 g), andphotoinitiator Irgacure 819 (0.004 g, 0.25 weight %) were blended andmixed together. The monomer mix obtained was degassed in an argonenvironment. The monomer mix was injected into the cavity in atransparent plastic (front curve side: Zeonor, base curve side:polypropylene) mold with a lens shape in a glove box under a nitrogengas environment, and a lens was obtained by irradiating with light(Philips TL03, 1.6 mW/cm2, 15 minutes) to harden. The lens obtained waspeeled from the mold and impurities such as residual monomer wereextracted by immersing for 70 minutes at room temperature in a 70%(volumetric ratio) aqueous solution of 2-propanol (IPA). After immersingin water for 10 minutes, the sample was placed submerged in a boric acidbuffer solution (pH 7.1 to 7.3) in a 5 mL vial bottle, and the vialbottle was placed in an autoclave and boiled for 30 minutes at 120° C.

The whole light transmissivity, water content, elastic modulus, andelongation of the lens sample obtained were as shown in Table 1, andthus a lens was obtained which was transparent and had a balance betweenfavorable physical properties.

Working Example 8

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the silicone acrylamide monomer of the followingformula (s3)

obtained by working example 2 was used as the silicone acrylamidemonomer in place of the monomer expressed by formula (s2). The wholelight transmissivity, water content, elastic modulus, and elongation ofthe lens sample obtained were as shown in Table 1, and thus a lens wasobtained which was transparent and had a balance between favorablephysical properties.

Working Example 9

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the silicone acrylamide monomer of the followingformula (s4)

obtained by Working Example 3 was used as the silicone acrylamidemonomer in place of the monomer expressed by formula (s2), and exceptthat the content of monomer mix was as follows; silicone acrylamidemonomer (s4) (0.925 g, 56.06 weight %), N,N-dimethyl acrylamide (0.552g, 33.27 weight %), the hydrophilic acrylamide monomer (h1) (0.116 g, 7weight %), N,N′-methylene bisacrylamide (MBA, 0.0 18 g, 1.10 weight %),UV absorber2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole (0.0 36 g,2.20 weight %), 3-methyl-3-pentanol (3M3P, 1.350 g), and photoinitiatorIrgacure 819 (0.004 g, 0.25 weight %). The whole light transmissivity,water content, elastic modulus, and elongation of the lens sampleobtained were as shown in Table 1, and thus a lens was obtained whichwas relatively transparent and had a balance between favorablemechanical properties. Wettability as measured by contact angle washigher than generally desired.

Working Example 10

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the content of monomer mix was as follows;silicone acrylamide monomer (s2) (1.21 g, 55 weight %), N,N-dimethylacrylamide (0.78 g, 35.53 weight %), polyvinyl pyrrolidone (PVP K90,0.088 g, 4 weight %), tetraethylene glycol dimethacrylate (TEGMA, 0.066g, 3 weight %), UV absorber2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole (0.048 g,2.20 weight %), 3-methyl-3-pentanol (3M3P, 1.80 g), and photoinitiatorIrgacure 819 (0.006 g, 0.25 weight %). The whole light transmissivity,water content, elastic modulus, and elongation of the lens sampleobtained were as shown in Table 1, and thus a lens was obtained. Watercontent and mechanical properties were favorable, but whole lenstransmissivity was low indicating an undesirably hazy lens and contactangle was higher than generally desired.

Working Example 11

A lens shaped sample was fabricated in a manner similar to WorkingExample 10, except that the silicone acrylamide monomer expressed by theformula (s3) was used as the silicone acrylamide monomer in place of themonomer expressed by formula (s2). The whole light transmissivity, watercontent, elastic modulus, and elongation of the lens sample obtainedwere as shown in Table 1, and thus a lens was obtained. Water contentand mechanical properties were favorable (including a desirable lowmodulus), and whole lens transmissivity was improved compared to WorkingExample 10. Contact angle was higher than generally desired.

Working Example 12

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the content of monomer mix was as follows;silicone acrylamide monomer (s2) (1.21 g, 55 weight %), N,N-dimethylacrylamide (0.43 g, 19.53 weight %), 2-hydroxyethyl methacrylate (0.176g, 8 weight %), polyvinyl pyrrolidone (PVP K90, 0.264 g, 12 weight %),tetraethylene glycol dimethacrylate (TEGMA, 0.066 g, 3 weight %), UVabsorber 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole(0.048 g, 2.20 weight %), 3-methyl-3-pentanol (3M3P, 1.80 g), andphotoinitiator Irgacure 819 (0.006 g, 0.25 weight %). The whole lighttransmissivity, water content, elastic modulus, and elongation of thelens sample obtained were as shown in Table 1, and thus a lens wasobtained which was transparent and had a balance between favorablephysical properties.

Working Example 13

A lens shaped sample was fabricated in a manner similar to WorkingExample 12, except that the silicone acrylamide monomer expressed by theformula (s3) was used as the silicone acrylamide monomer in place of themonomer expressed by formula (s2). The whole light transmissivity, watercontent, elastic modulus, and elongation of the lens sample obtainedwere as shown in Table 1, and thus a lens was obtained which wastransparent and had a balance between favorable physical properties.

Working Example 14

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the silicone acrylamide monomer of the followingformula (s5)

obtained by Working Example 18 was used as the silicone acrylamidemonomer in place of the monomer expressed by formula (s2), and exceptthat the content of monomer mix was as follows; silicone acrylamidemonomer (s5) (0.925 g, 56.06 weight %), N,N-dimethyl acrylamide (0.419g, 25.27 weight %), polyvinyl pyrrolidone (PVP K90, 0.132 g, 8 weight%), the hydrophilic acrylamide monomer (h1) (0.116 g, 7 weight %),N,N′-methylene bisacrylamide (MBA, 0.0 18 g, 1.10 weight %), UV absorber2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole (0.0 36 g,2.20 weight %), t-amyl alcohol (TAA, 1.350 g), and photoinitiatorIrgacure 819 (0.004 g, 0.25 weight %). The whole light transmissivity,water content, elastic modulus, and elongation of the lens sampleobtained were as shown in Table 1, and thus a lens was obtained whichhad a balance of favorable physical properties including a desirablemodulus. Whole lens transmissivity was low indicating an undesirablyhazy lens.

Working Example 15

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that silicone acrylamide monomer of the followingformula (s6)

obtained by Working Example 18 was used as the silicone acrylamidemonomer in place of the monomer expressed by formula (s2), and exceptthat the content of monomer mix was as follows; silicone acrylamidemonomer (s6) (0.925 g, 56.06 weight %), N,N-dimethyl acrylamide (0.419g, 25.27 weight %), polyvinyl pyrrolidone (PVP K90, 0.132 g, 8 weight%), the hydrophilic acrylamide monomer (h1) (0.116 g, 7 weight %),N,N′-methylene bisacrylamide (MBA, 0.0 18 g, 1.10 weight %), UV absorber2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole (0.0 36 g,2.20 weight %), t-amyl alcohol (TAA, 1.350 g), and photoinitiatorIrgacure 819 (0.004 g, 0.25 weight %). The whole light transmissivity,water content, elastic modulus, and elongation of the lens sampleobtained were as shown in Table 1, and thus a lens was obtained whichhad a balance of favorable physical properties, including a desirablemodulus. Whole lens transmissivity was low indicating an undesirablyhazy lens.

Comparative Example 1

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the silicone acrylamide monomer of the followingformula (t1) (made according to Examples 1 and 2 of WO05/078482A1)

was used as the silicone acrylamide monomer in place of the monomerexpressed by formula (s2). The whole light transmissivity, watercontent, elastic modulus, and elongation of the lens shaped sampleobtained were as shown in Table 1, and the stress zero time was over 1second, indicating that the shape recovery properties were notsufficient.

Comparative Example 2

A lens shaped sample was fabricated in a manner similar to workingexample 7, except that the silicone acrylamide monomer of the followingformula (t2) (made according to Examples 5 and 6 of WO05/078482A1)

was used as the silicone acrylamide monomer in place of the monomerexpressed by formula (s2). The whole light transmissivity, watercontent, elastic modulus, and elongation of the lens shaped sampleobtained were as shown in Table 1, and the stress zero time was over 1second, indicating that the shape recovery properties were notsufficient.

Synthesis Example 16

The compound obtained by the same method as synthesis example 6 (20.0 g,0.072 mol), bis(trimethylsiloxy)methylsilane (16 g, 0.072 mol), toluene(150 mL), and platinum tetra solution (200 μL) were placed in a 500 mL3-necked flask and a reflex condenser, thermometer, and mechanicalstirrer were attached. The reaction was performed at 120° C. for 2hours. The reaction solution was concentrated in an evaporator, and thenpurified by distillation under reduced pressure (full vac., 160° C.).The yield was 21.13 g (58.7% yield) and the GC purity was 95.7%.

Synthesis Example 17

The compound obtained by synthesis example 16 (20 g, 0.040 mol),triethylamine (8.14 g, 0.040 mol), and ethyl acetate (130 mL) wereplaced in a 500 mL 3-necked flask and a dropping funnel, thermometer,and mechanical stirrer were attached. Acryloyl chloride (7.28 g, 0.040mol) and ethyl acetate (100 mL) were placed in the dropping funnel. The3-necked flask was placed in an ice bath containing salt and dropwiseaddition was started after waiting for the internal temperature to dropto 0° C. While maintaining the internal temperature between −2 and 3°C., dropwise addition was performed over approximately 2 hours and afterdropwise addition was completed, the reaction was continued for anotherhour and then terminated. The solution was then filtered while washingwith a small amount of chilled ethyl acetate that had been chilled in arefrigerator. The filtrate was transferred to a separation funnel and400 mL of hexane was added. The solution was washed two times with water(180 mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (180 mL), and two times with a saturated aqueous solution ofsodium chloride (180 mL). Anhydrous sodium sulfate was added to theorganic layer and drying was performed overnight. After filtering, thissolution was concentrated in an evaporator to obtain crude product. Thecrude yield was 27.5 g (125% crude yield).

Synthesis Example 18

The crude product obtained by synthesis example 17 (26.5 g, 0.048 mol),3 parts (weight ratio) of methanol (79.5 g) and one half part (weightratio) of acetic acid (13.3 g) was added for each part of crude product,and then the solution was mixed for 1 hour at 40° C. After reacting, thesolution was concentrated in an evaporator. The liquid obtained (48.5 g)was transferred to a separation funnel, and 4 parts of hexane(volumetric ratio) (190 g) were added to one part of liquid. Thesolution was washed two times each with water (140 mL), a saturatedaqueous solution of sodium hydrogen carbonate (140 mL), and a saturatedaqueous solution of sodium chloride (170 mL), and then the organic layerwas dried overnight using anhydrous sodium sulfate. The solution wasconcentrated in an evaporator to obtain 16.0 g of crude material. 16.0 gof the crude material was purified in a column. The amount of silica gelused was five times the weight of the crude material (80 g). For thesolvent, hexane/ethyl acetate=2/1 was used until impurities weredischarged (500 mL), and after confirming that the impurities had beendischarged, the target material was eluted using hexane/ethylacetate=1/2 (750 mL). The range of the fraction containing the targetmaterial was confirmed using TLC, and several fractions on both ends ofthis range were measured by GC, and only fractions where the byproductswere less than 1% were collected. 15 mg of BHT was added and thesolution was concentrated in an evaporator. The solution was stirred at60° C. while reducing the pressure using a vacuum pump for 1 hour inorder to remove the remaining solvent, and it was confirmed that aresidual solvent peak was not observed using NMR. The yield was 7.5 g(38.3% yield) and the GC purity was 97.7%.

Synthesis Example 19

3-Aminopropyltris(trimethylsiloxy)silane (49 g, 0.14 mol) was placed ina 3-necked flask and a reflex condenser, thermometer, and droppingfunnel were attached. Glycidol (2,3-epoxy-1-propanol, 3.5 g, 0.05 mol)was added to the dropping funnel, and added by drops over approximately40 minutes while mixing at 30° C. A GC measurement was performed eachhour starting at the time that dropwise addition was completed in orderto confirm the progress of the reaction. 20 hours after dropwiseaddition was completed it was confirmed that the glycidol peak was 1% orless and the reaction was terminated. The solution was concentrated inan evaporator, and then purified by reduced pressure installation (fullvac, by 190° C.). The yield was 13.65 g (67.8% yield), and the GC puritywas 92.8%.

Synthesis Example 20

The compound obtained in synthesis example 19 (12.5 g, 0.03 mol),hexamethyldisilazane (10. g, 0.06 mol), and saccharine (250 mg) wereplaced in a 3-necked flask and a reflex condenser, and thermometer,mechanical stirrer were attached. The reaction was performed for 2 hoursat 100° C. and the reaction was terminated after confirming that thereactants were reduced or exhausted using GC. The reaction solution wasconcentrated in an evaporator, and then purified by distillation underreduced pressure (full vac, by 170° C.). The yield was 13.3 g (76%yield), and the GC purity was 89.5%.

Synthesis Example 21

The compound obtained by synthesis example 20 (13.0 g, 0.023 mol),triethylamine (2.33 g, 0.023 mol), and ethyl acetate (50 mL) were placedin a 1 L 3-necked flask and a dropping funnel, thermometer, andmechanical stirrer were attached. Acryloyl chloride (2.1 g, 0.023 mol)and ethyl acetate (10 mL) were placed in the dropping funnel. The3-necked flask was placed in an ice bath containing salt and dropwiseaddition was started after waiting for the internal temperature to dropto 0° C. While maintaining the internal temperature between −2 and 3°C., dropwise addition was performed over approximately 1 hour and afterdropwise addition was completed, the reaction was continued for anotherhour and then terminated. The solution was then filtered while washingwith a small amount of chilled ethyl acetate that had been chilled in arefrigerator. The filtrate was transferred to a separation funnel and 60mL of hexane was added. The solution was washed two times with water (50mL), two times with a saturated aqueous solution of sodium hydrogencarbonate (50 mL), and two times with a saturated aqueous solution ofsodium chloride (50 mL). Anhydrous sodium sulfate was added to theorganic layer and drying was performed overnight. After filtering, thissolution was concentrated in an evaporator to obtain crude product. Thecrude yield was 14.2 g and the GC purity was 86.1%.

Synthesis Example 22

The crude product obtained by synthesis example 21 (14.0 g), 3 parts(weight ratio) of methanol (42.0 g) and one half part (weight ratio) ofacetic acid (7.0 g) was added for each part of crude product, and thenthe solution was mixed for 4 hour at 40° C. After reacting, the solutionwas concentrated in an evaporator. The liquid obtained (16.95 g) wastransferred to a separation funnel, and 4 parts of hexane (volumetricratio) (68.0 g) were added to one part of liquid. The solution waswashed two times each with water (50 mL), a saturated aqueous solutionof sodium hydrogen carbonate (50 mL), and a saturated aqueous solutionof sodium chloride (50 mL), and then the organic layer was driedovernight using anhydrous sodium sulfate. The solution was concentratedin an evaporator to obtain 9.95 g of crude material. 9.5 g of the crudematerial was purified in a column. The amount of silica gel used wasfive times the weight of the crude material (50 g). For the solvent,hexane/ethyl acetate=2/1 was used until impurities were discharged (300mL), and after confirming that the impurities had been discharged, thetarget material was eluted using hexane/ethyl acetate=1/1 (500 mL). Therange of the fraction containing the target material was confirmed usingTLC, and several fractions on both ends of this range were measured byGC, and only fractions where the byproducts were less than 1% werecollected. 4.8 mg of BHT was added and the solution was concentrated inan evaporator. The solution was stirred at 60° C. while reducing thepressure using a vacuum pump for 1 hour in order to remove the remainingsolvent, and it was confirmed that a residual solvent peak was notobserved using NMR. The yield was 3.14 g (28% yield) and the GC puritywas 97.8%.

Comparative Example 3

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the silicone acrylamide monomer of the followingformula (t3)

obtained by Synthesis Example 16 was used as the silicone acrylamidemonomer in place of the monomer expressed by formula (s2). The wholelight transmissivity, water content, elastic modulus, and elongation ofthe lens shaped sample obtained were as shown in Table 1, and the stresszero time was over 1 second, indicating that the shape recoveryproperties were not sufficient.

Comparative Example 4

A lens shaped sample was fabricated in a manner similar to WorkingExample 7, except that the following formula (t4), obtained by SynthesisExample 17

was used as the silicone acrylamide monomer in place of the monomerexpressed by formula (s2). The whole light transmissivity, watercontent, elastic modulus, and elongation of the lens shaped sampleobtained were as shown in Table 1, and the stress zero time was over 1second, indicating that the shape recovery properties were notsufficient.

TABLE 1 Center water elastic stress zero Advancing Silicone thicknessDiameter Transmissivity content elongation modulus time contact anglemonomer (μM) (mm) (%) (%) (%) (psi) (sec) (°) Working Example Formula137 13.0 89.0 42.4 254 95 0.89 46 7 (s2) Working Example Formula 13412.7 91.9 38.7 197 109 0.76 28 8 (s3) Working Example Formula 135 12.987.5 43.5 215 87 0.84 98 9 (s4) Working Example Formula 144 14.1 31.348.4 363 61 0.74 89 10 (s2) Working Example Formula 145 14.5 52.4 49.4354 88 0.89 81 11 (s3) Working Example Formula 146 13.9 89.9 51.4 267 860.89 59 12 (s2) Working Example Formula 149 14.1 89.3 51.9 187 114 0.9248 13 (s3) Working Example Formula 87 NA 6.6 44.3 238 74 0.99 NA 14 (s5)Working Example Formula 92 NA 7.2 43.3 293 81 0.98 NA 15 (s6)Comparative Formula 142 13.4 89.1 45.7 334 85 1.07 38 Example 1 (t1)Comparative Formula 143 13.2 91.4 41.3 265 145 1.24 47 Example 2 (t2)Comparative Formula 144 13.2 90.7 42.8 240 438 2.65 40 Example 3 (t3)Comparative Formula 141 12.7 89.4 36.2 169 705 2.95 38 Example 4 (t4)

Working Example 16 Through 19

A lens sample was fabricated in a manner similar to Working Example 7,except that 2-hydroxyethyl methacrylamide (HEMAA-purchased from MonomerPolymer Dajac Laboratories, PA) expressed by the formula (h5)

was used in place of the monomer expressed by formula (h1) as thenon-silicone acrylamide monomer, and except that the silicone monomerand the composition of the silicone monomer, the non-silicone acrylamideand N,N-dimethylacrylamide were changed as shown in Table 2. Theappearance, whole light transmissivity, water content, elastic modulus,and elongation of the sample obtained were as shown in Table 2.

TABLE 2 N,N- silicone non-silicone dimethylacryl water elastic stressAdvancing acrylamide acrylamide amide transmissivity content moduluselongation zero time contact angle formula (wt %) formula (wt %) (wt %)(%) (%) (psi) (%) (sec) (degree) Working (s2) 56.06 (h5) 7 25.27 55.145.7 147 133 0.83 61.1 Example 16 Working (s2) 56.06 (h5) 12 20.27 84.741.6 165 127 0.87 65.9 Example 17 Working (s3) 56.06 (h5) 7 25.27 91.939.8 192 162 0.88 66.7 Example 18 Working (s3) 56.06 (h5) 12 20.27 91.139.2 201 170 0.99 77.0 Example 19

Working Example 20

A monomer mix was prepared in the following molar ratio: the monomerexpressed by formula (s2) (32.4 mol %), N,N′ dimethyl acrylamide (32.5mol %), N-(2-hydroxyethyl)acrylamide (32.4 mol %), N,N′ methylenebisacrylacrylamide (2.4 mol %), and photoinitiator Irgacure 819 (0.2 mol%). Into the monomer mix (55 weight %), tripropylene glycol methyl ether(TPME, 40 weight %) and polyvinyl pyrrolidone (PVP K90, 5 weight %) wereadded.

Polymerization of the monomer mix was carried out at 70° C. under drynitrogen using an LED light source (˜420 nm, 4.0 mW/cm²) for 10 minutes,using the DSC procedure described above.

The polymerization rate of the monomer mix was analyzed by photo DSC,which was shown in FIG. 1 as “SA1 RMM”. The rate was much faster thanthat of Comparative Example 5.

Working Example 21

A monomer mix was prepared in a manner similar to Working Example 20,except that the monomer expressed by the formula (s3) was used assilicone acrylamide monomer in place of the monomer expressed by theformula (s2).

The polymerization rate of the monomer mix was analyzed by photo DSC,which was shown in FIG. 1 as “SA2 RMM”. The rate was much faster thanthat of Comparative Example 5.

Comparative Example 5

A monomer mix was prepared in a manner similar to Working Example 20,except that the silicone methacrylate monomer expressed by the followingformula (u1) (made according to Example 29 of WO2008/005229)

was used in place of the silicone acrylamide monomer expressed by theformula (s2), except that 2-hydroxyethyl methacrylate was used in placeof 2-hydroxyethylacrylamide, and except that tetraethylene glycoldimethacrylate was used in place of N,N′-methylenebisacrylamide. Thesemonomers were used in the same molar ratio as Working Example 20.

The polymerization rate of the monomer mix was analyzed by photo DSC,which was shown in FIG. 1 as “OH mPDMS RMM”.

The invention claimed is:
 1. A silicone (meth)acrylamide monomer of theformula


2. A polymer obtained by polymerizing a monomer mixture comprising asilicone (meth)acrylamide monomer according to claim
 1. 3. A polymeraccording to claim 1, wherein the monomer mixture further comprisesN-(mono-hydroxyl substituted C1-C20 alkyl)methacrylamide orN-(mono-hydroxyl substituted C6-C20 aryl)methacrylamide.
 4. Anophthalmic lens, comprising a polymer according to claim 1 or
 2. 5. Acontact lens, comprising a polymer according to claim 1 or 2.